Aromatic halocarbyl chemical products



Unitcd States Patent Ofifice 3,093,677 Patented June 11, 1963 3,093,677 AROMATIC HALOCARBYL CHEMICAL PRODUCTS Elmore L. Martin, Wilmington, DeL, assignor to E. I. du Pont de Nelnonrs and Company, Wilmington, Del., .a corporation of Delaware No Drawing. Filed Aug. 28, 1959, Ser. No. 836,601 13 Claims. ((21. 260-465) Ihis invention relates to new dyestufis and to their 7 The rapid advances which have been made in textile focused attention on the need to provide dycstufis which are light and wash-fast, which cover all or was re the entire visible spectrum, and which can be applied to natural fibers and to the newer synthetics with minim, of application variations. The provision of such d has been a long standing research objective,

tonow has remained unattained.

An, of the present invention is, consequently, provision of certain novel and useful dyestuffs.

Another obiect of the invention is provision of a process for making the aforesaid novel dyestufis.

In the furtherance of the composition of matter aspects of the invention, there is now provided a new class of dyestufis corresponding to the formula in which X and X individually or together are perhalocarbyl and oxoperhalocarbyl; Y is a negative or electronattracting group; and Q is a color-forming group, i.e., a monovalent organic radical such that the corresponding QH compound is capable of condensing with benzene diazonium chloride to form an azo dye.

More detailed definitions of the symbols of the above formula are as follows:

(a) X and X alike or dilferent, are separately, monovalent perhalocarbyl or oxoperhalocarbyl radicals of generally no more than 12 carbons or, joined together, divalent perhalocarbyl or oxoperhalocarbyl radieels of generally 2-6 carbons forming with the depicted carbons a carbocyclic ring of 4-8 carbons. Any oxocarbonyl oxygen present is carried by a carbon joined to one of the depicted doubly bonded carbons.

Pcrhalocarbyl as used herein refers to organic radicals composed solely of carbon and halogen. Oxoperhalocarby refers'to organic radicals which contain otdy carbon, halogen, and oxocarbonyl oxygen. Exemplary perha-iocarbyl radicals are perchloroand perfluorcethyl, perchloropropyl, perbromomethyl, periiuorodecyl, perchlonoisobutyl, periluorotrimethylene, perchlorotetramethylene, l,l,4,4 tetrafiuoro 2,3 dichloro 2 butenylcne, and the like. Exemplary oxoperhalocarbyl radicals are 2,2,3,3,3 pentachloropropionyl, 2,3 dichloro 1,4- dioxo 2 butenylene, perchloroadipoyl, perchloroacetyl, perfiuorosuccinyl, and the like;

(b) Y is an elecnonegative radical of the group consisting of cyano, nitro, alkylsulfon-yl, alkarylsulfonyl, arylsulfonyl, aralkylsulfonyl, carboxy, alkoxycarbonyl, carbamyl, halocanbonyl and acyl (i.e., alkylcarbouyl), all of generally no more than 12. and preferably no more than 8 carbons; and

(c) Q is a radical that may defined in terms of the compound QH from which it is derived. QH is any orpound QH which reacts with benzene diazonium chloride to form an azo dye.

The same hydrogen may be replaced both in the diazo reaction and in that of this invention. 7

The definition of Q flows from the fact, evident below, that the compounds have the same capacity for coupling with color formers (i.e., QI-I cmnpounds) as do the aryl diazonium salts. The coupling reactions of the aryl d-iazonium salts are well known and are discussed in detail by K. H. Saunders in The Aromatic Diazo Compounds and Their Technical Applications, Edward Arnold & Co., London (1949), See. Ed., pp. 194-221. See also H. A. Lubs, The Chemistry of Synthetic Dyes and Pigments, Reinhold Company, New York 1955), Sec. Ed., pp.

The definition of QR is based specifically on the ability to couple with benzene diazonium chloride partly because diazonium chloride is the simplest and most readily available of the aryl diazonium chlorides and partly because such a definition points out that hydrocarbon compounds such as benzene and monoalkoxy benzenes are not included among the color formers. Benzene and anisole, for example, will react with certain highly activated aryl diazonium halides but not with benzene diazonium chloride to yield azo dyes.

The test to determine reactivity with benzene dlazonium "chloride may be conducted as follows:

Benzene diazonium chloride is prepared by treating one molar equivalent of aniline with 2.7 molecular equivalents of hydrogen chloride as a concentrated aqueous solution. This solution is cooled to 0 C. and treated with one molecular equivalent of sodium nitrite, dissolved in twice its weight of water. The addition of the nitrite solution is carried out at a rate so that the temperature does not exceed 5 C. To ten milligrams of compound QH dissolved in one to two ml. of acetone there is added about 0.25 g. of sodium acetate. One to three drops of the diazonium solution are then added to the test mixture. When QI-I contains an electron-donating group or is an active methylene compound, the addition of the benzene diazom'um chloride causes immediate formation of an azo dye ranging in color from deep orange through red-purple to green. An alternative method for expressing the result is that there is formed an azo compound having at least one absorption peak between 350 and 750 millimicrons.

QH compounds usefully ernployable in the present invcntion are of two kinds, namely (1) those aromatic compounds containing electron donating groups and (2) compounds containing active methylene groups.

In preferred QH compounds, Q may be R NAr-, ROONHNRAr- RCH===NN-RAI,

OH and R0 in which Ar is arylene; R and R" are hydrogen or hydrocarbyl; R is hydrocarbyl, beta-alkoxyethyl, beta-acyloxyethyl, beta-cyanoethyl, or beta-trialkylammonium ethyl; B and B are --CN, -COOR, COR, CONR CSNR --SO R, --NO 'NR and SR=+; D is alkyl, halogen, -SO Na, or B; D is hydrogen or D, with the proviso D and R" taken together may form another aryl ring; and n is 0 or i. In a given compound the several embodiments of R and R that may be involved may be the same or different.

Aryl and arylene refer, respectively, to monovalent and to divalent aromatic radicals. In the latter the divalency stems from different carbon atoms. Among the aryl and arylene radicals are included those from which the corresponding aromatic compound obtained by placing hydrogen at the respective bonds of the aryl or arylene group has a resonance energy of not less than 20 kcal./ mole. Resonance energies of organic compounds and the determination of resonance energy is shown by Linus Pauling in The Nature of the Chemical Bond, Sec. Ed, Cornell University Press, 1945, pages 132-139.

Aryl groups particularly suited are phenyl, naphthyl, anthryl, phenanthryl, benzpyryl, trypticyl, furyl, thienyl, pyrrolyl, and the corresponding arylene groups phenylene, naphthylene, anthrylene, furylene, thienylene, and pyrrolylene.

Hydrocarbyl refers to any monovalent organic radical composed solely of carbon and hydrogen. The hydrocarbyl groups can be alkyl, cycloalkyl, aryl, aralkyl, alkaryl, single ring, multiple ring, straight chain, branched chain, large or small. The widest variation does not detract from the fundamental characteristics of the hydrocarbyl radical of passing unchanged in the process by which the products of this invention are made. In general, hydrocarbyl groups containing not more than 20 carbon atoms are most available and to that extent are preferred. There is no question of the operability of and the intent to include and disclose all hydrocarbyl groups whatsoever.

QH compounds containing an active methylene group, e.g., BB'CH-, above, are those compounds which contain the methylene group adjacent to two carbonyl or other strongly electron-attracting groups. This methylene group is discussed by Saunders, op. cit., pp. 207- 217, is mentioned by Lubs, op. cit., pp. 101 and 102, and is well known to workers in the azo dye art as a site of coupling reactions. Compounds containing active methylene groups are at least partly aliphatic in nature. When the active methylene group is adjacent to a carbonyl group, the compound is capable of existing in the tautomeric keto-enol form. Coupling in the process of the present invention is through the active methylene group, one of the hydrogens being substituted.

The process aspects of this invention may be illustrated schematically as follows:

In these equations A and Z are halogen of atomic num her 9 through 35, i.e., fluorine, chlorine, or bromine; Q, X X and Y have the previously-indicated meanings; and M is a metal, preferably an alkali metal such as sodium or potassium.

The process of the invention may be accomplished simply by adding the various starting materials together and separating the resultant colored product by obvious means. There are no particularly critical process variables involved. It is to be understood, however, that the intermediate product AC=CY 2'0 X need not be isolated, i.e., the process can be carried out by mixing all of the reactants initially. Likewise, if desired, intermediate A-C=OY i.

can be prepared separately and then reacted in a separate operation with compound QH.

It is convenient, but not necessary, to etfect the reaction between compound A-O=C-Z 1'0 X: and compound MY and QH in a reaction medium inert to the reactants and to the products. Suitable media are aliphatic and aromatic hydrocarbons, dialkyl ethers, cyclic esters, e.g., dioxane and tetrahydrofuran, N-alkyl acylamides, e.g., dimethyland diethylformamides, N- methylformamide, N-rnethyl-Nethylacetamide, N,N-dimethylacetamide, N,N diethylacetamide, N methylformanilide, etc., tetramethylurea, tetraethylurea, pyridine, dimethylsulfoxide, acetonitrile, etc., nitrosodimethylamine, and trifiuoroethanol. In general, the inert medium is used to facilitate the dissipation of heat from the slightly exothermic reaction.

As previously stated, M in MY is a metal, preferably an alkali metal such as sodium, potassium, and lithium. MY compounds in which M is sodium are generally used because of the lower cost of sodium as compared to the other alkali metals.

The temperature at which the reaction is carried out can be varied widely, e.g., from below 10 C. up to the decomposition temperature of the reactants or products. As a rule, the best results from the standpoint of product yield and reaction rate are achieved at temperatures of from 0 C. to C. and this range embraces the conditions most generally used. Pressure is not a critical variable and ambient atmospheric pressure is generally used for convenience, although pressures above or below can be employed, if desired. The time of the reaction is dependent upon the particular reactants employed and can vary up to one hour or more.

Complete reaction between compound and compounds OH and MY, of course, requires the use of at least equimolar quantities of each reactant. This fact, however, in no way limits the molar proportions of these reactants and the relative amounts of each can be varied widely. Generally the use of a large excess of one or other of the reactants have little value in improving product yield. For that reason, approximately equirnolar quantities are usually employed. Exemplary compounds of the formula usable in the process of the invention are shown in Table (VII) (XII) OKIII) (XIV) (XVII) (XV III) xxx) F F F F F F F F Fr Fl (XXIV) (XXV) aixvn F1 Fl our) Cl-O=O--SO|OnHCH|(P) (P)CHICBHQ:S/

O --GCsHcN (CHI 01 Ol 5 x111) Ol--C=ONO| /0=0 01 Ol Oh- --O-0h (IV) (XIV) ClC=C-s0:OH|CB 5 0 A solution of 2.34 g. of tetrachlorocyclopentene-L3- i dione (I), prepared as described in I. Am. Chem. Soc. Representative usable QH compounds of the aromatic 489 m 25 dunethylformamlde was type are: ZGdimethYlPhenol; 1 acetyl 2 methyl 2 pheny1 cooled to 15 C. 'I'o the solution there was added 2.4 g. hydrazine; sodium l-naphthol-Z-sulfonate; N-allyl-N- of NN'dmethylamlme (11,1)! followed by of finely methylaniline; N,N dibenzylaniline; N cyclohexyI-N- Powdered anhydrmfs, sodium P91118116 sulfinaw methylaniline; N-methyl-N-propargylaniline; N,N.di h 1- 'Ihroughout the addition of the sodium p-toluenesulfinate alpha-naphthylamine; N,N di(betaethoxyethyDaniline; the timperamm of the manure was 13 9* 15 N,N-di(beta-acctoxyethyl)aniline; N,N-dimethy1aniline; to 20 C. by means of external cooling. After stlrrmg for N,N-dioctadecylaniline; N (beta benzoyloxyethyl)-N- 9 i0 the a fl mixture was methylaniline; 3-mcthylsalicy1amide of m-aminobenzalde- (muted W131 Petroleum ethal' Watef- Tha resulting hyde ethylene glycol acetal; beta-(N-ethylanilino)ethylsolid as ak n up in m t y chloride, the lu n trimethylammonium chloride; beta-(N-dodecylanilino) was concentrated to a small volume, and anhydrous ether ethyldimethylamine hydrochloride; beta-(Ncthyl-alphawas added. The crystalline material was collected and re- P y )et y tricthylammonium chloride; and the crystallized three additional times. There was obtained like. 0.9 g. of a black crystalline compound (IV) melting at Representaflve Q compounds contamins astwe 167 to 169 0., having a molecular extinction coeflimethylene groups are acetoacetlc ester and its annd f cient 24,600 at 562 m and identified as Q,2-dich1oro-4- the ester, nltrlle, amide, and mixed functions of malonlc (pdimethylamino) 5 (p to1uene sulfonyl) cyclopentane acid; acetylacetone; acetonedlcanboxyllc acid, its esters 1,3 dione and amides cycllc l,3-d1k etones; beta-ketonltr le-s; beta- Anatysm Calcd f C H O NSCI C, 54.79%; H, sulfonyl n1tr1les;cyanoacetlc ester; cyanoacetamldes; beta- 3 cl 16 197 Found. C 54 79% H 4 12% Cl nitronitriles; beta-nitrocsters; malononitrile dimer; 3-(2- furyl)acro1ein dimethylhydrazone; and the like.

There follow some examples which illustrate, but are Examples 2. not intended to limit, the invention.

Example 1 40 Table III summarizes a series of experiments in which 5 g. of the coupler shown in column 2 is dissolved in +NaO:S-Ce |C a(D) OIHIN(CH1)B 472 g. of N,Ndimethylformamide and heated in turn 0: =0 with 5 g. of QH compound (column 3) and 5 g. of com- 0 pound MY (column 4). The mixture is then warmed on 3( the steam bath for a few minutes, during which time the (I) (m (m) compound shown in column 5 is formed.

TABLE III QH Ex. Coupler (color- MY Product Color (A man-m former) A--C=CZ Q 2 ClO==G--Ol A C I D-(OHI)INCBHAC=CON' Orange-red (530).

(F: )I ((51%): a l

1 l l C] 3 C1-C=C-Cl A C IJ(OHI):NCQH4C=CCN- Red (503:370).

OFl Fl Fl F: 4 ClC=C-Cl A C P'(CH:)lNCn A- Red (550:300).

F: F: F: F: Cl 01 01 =t zol 6 C1C==OOl A D -(cH. ,NC.H.-C=0S0,0,H.CH, Yellow F: F; F: Fl 0 ClC=O-Cl B 0 lD-(CH NCnH4]:=C=CH Pale green (--)t F; Fl =C-CN Fl 21F:

7 CIO====C-Cl A C p-(OHa)|NC H C=C-CN Red F1 Fl F: (ilFs CF: CF:

See footnote at end or table.

El. Coupler (o o r- MY Product Color (A man-m tor-mar) AC=C--Z Q-O=C-Y I. a l 1* 3 8--.--- Gl-C==C-Ol A C p-(CHi):NCiH.-C=C0N Red (-J.

m Table III, A, standirm alone, represents N ,N-dimethyianillne; B, 1,1-b1s(p-dimethylaminopheny!)ethylene; Q sodium cyanide; and D, sodium p-methylphenylsulflnate.

Table IV summarizes a series of experiments in which 0.0005 mole of the coupler and 0.0005 mole of the QH compound were dissolved in 3-4 g. of N,N-dimethylformamide. To this solution there was then added 0.0005 mole Examples 9-26 of MY compound. The reaction mixture was stirred at room temperature for several minutes. During this time the reaction mixture developed the color shown in coiumn 5. Slight warming in a bath at 40-50 C. increased the rate of color formation in those instances where it was slow in developing at room temperature.

See tootnote at end of table.

I In Table IV, A, standing alone, represents N,N-dimet,hylaniline; B, 1,l-bls(p-dimethylaminophony!)eth lene; D, sodium -meth l hen l lfln E, sodium methylsulfinate; F, sodium butylsulfinate; G, sodium nitrite; and H, sodium benzylsulflnate. y p y p y su ate in the second columns.

information for some representative active methylenic compounds. In these two tables the generic formula of cule except Q, i.e.,

Table VI sets forth the same the product molecule may be written Q a u r- :(D) o=$ =0 Q being as defined above. B represents all of the mole- TABLE V Example QH (color-ionizer) Product HJC 27 N-methyl-Nfl-cyauo-ethylanfline I HB NC-CHrC 28 Furylacroleinphenylhydmmna 0sH:-NHN=CHCH=0Hl0 B 29 Pynole-Z-aldehyde dimethylhydrazona (C x)rN-N=CHlNJ' -B 1 30 1-benzoyl-2-pheny1hydrazine fls--IITH N-B JJsHs I I B 31 1,2,5-trimethy1pyrrole t -L 1 013:

SOaNa 32 Bodiumsalt oI1-naphthol-2-su1ionieaeid HOB 33 p-Methoxybenzaldehyde-p-methoxyanil, H:0-0-CH;NJB

H|COCuH4I' 34 N-n-butylcarbazole B 35 m-Diethylaminophenol aHahN B 9 G9 35 fl-(N-ethylanilinoethyl)trimethylammonium chloride Cl(CH|):N-CH1CH:N B

37 Benzaldehydebhenyihydrazon CH=NNH-B 38 1.l-bis(pdhnethylaminophenybethylene [(CH:):N]C=CHB 39 l-phenyI-S-methylpyrazolone CoH51I1'-C=O N -B CH; 40 2,6dimethy HOB 41 Resorcinol dimethyl ether emu-Q43 42 Indole (F4;

TABLE VI Er QH (color-former) Product 43- Malononitrile dimer (CN)aC=C(NH )CCH(CN)B 44..- Ethyl acetoacetate CHuCOCHB 45... Acetylacatone (CHaCOhOH-B 46-.. Malononitrile (CNhCH-B 47-.. Ethylcyanoacetate (CaHrOCO)CH-B 48- Acetoacetaullide CHaCOCH-B CONHCgH;

49.-- Diethyl malouate (CiHrO0C) CH-B (CzHsO C O) 50.-- Ethyl malouamate CH-B (HaNCO) (COOCzHa) 51-.. Dlethyl acetonedlcarbox- CH-B ylste.

CaHaOOCCHaCO 52.-- 1,3-eyclohexanedione B 53-.. 2 ethoxycarbonylcyclopentanone. c O 0 023 54-.. Aeetoaeetonitrile (OHaCO) (ON) 011-13 55... Methylsulfonylaceto- (OH;B0:)(GN)CHB nitrile. 4O 56.-- Cyanoaeetanilide (CONHCrH )(CN)CH-B 57... Ethyl nltroacetate (COOCzHa)(NOa)CHB 58.-. Nltroacetonitrile (ON) (NOr)CHB The compounds of this invention are colored and are useful as dyestuffs in all applications where dyestuffs are known to be useful, such as coloring pigments for plast cs, paints, and the like. They are also useful in the dyeing of textiles as shown below:

A dye bath is prepared using 10,000 g. of water containing 2 g. of a sulfonated lignin dispersant (Marasperse CB, Marathon Co.) and S g. of acetic acid. A

solution of 2 g. of 2,2-dichloro-4-(p-dimethylaminophenyl -5- (p-toluenesulfonyl) cyclopentenel ,3 -dione, prepared as in Example I, in 100 g. of acetone is added with stirring. The dye bath is heated at 8095' C. and swatches of cellulose acetate, nylon, silk, and wool weighing 10 g. each are added. After a few minutes the cellulose acetate fabric is dyed yellow and the nylon, silk, and wool are dyed brown. These dyeings have good lightand wash-resistance.

Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, I propose to be bound solely by the appended claims.

I claim:

1. A compound of the formula wherein: X and X are selected individually from the group consisting of monovalent perhalocarbyl and 0x0- perhalocarbyl radicals of up to 12 carbons and, jointly, from the group consisting of divalent perhalocarbyl and oxoperhalocarbyl radicals of up to 6 carbons, any oxocarbonyl oxygen being carried by a carbon joined to one of the depicted doubly bonded carbons; Y is an electronegative radical selected from the group consisting of cyano, nitro, carboxy, carbamyl, halocarbonyl, and alkylsulfonyl, alkarylsulfonyl, arylsulfonyl, aralkylsulfonyl, alkoxycarbonyl and alkylcarbony of up to 12 carbon atoms; and Q is the monovalent organic radical of a compound QH selected from the group consisting of aromatic compounds containing an electron-donating group other than methoxy and compounds containing an active methylene group.

2. The process of producing a compound of claim 2 which comprises reacting, at a temperature between about 10" and C.: (1) a compound of the formula wherein: A is halogen of atomic number 93S; X and X are selected individually from the group consisting of monovalent perhalocarb'yl and oxoperhalocarbyl radicals of up to 12 carbons and, jointly, from the group consisting of divalent perhalocarbyl and oxoperhalocarbyl radicals of up to 6 carbons, any oxocarbonyl oxygen being carried by a carbon joined to one of the depicted doubly bonded carbons; and Y is an electronegative radical selected from the group consisting of cyano, nitro, carboxy, carbamyl, halocarbonyl, and alkylcarbonyl of up to 12 carbon atoms; and (2) an organic compound QH selected from the group consisting of aromatic compounds containing an electron-donating group other than methoxy and compounds containing an active methylene group.

3. The process of claim 2 accomplished in an inert reaction medium.

4. The process which comprises reacting, at a temperature between about l0 and 100 C., tetrachlorocyclopentene-l,3-dione, N,N-dimethylaniline, and an alkali metal sulfinate.

S. The process which comprises reacting, at a temperature between about -l0 and 100 C., l,2-dichloro-l,2-bis- (w-chloroperfluoroethyl)ethylene, N,N dimethylaniline, and a metal cyanide.

6. The process which comprises reacting, at a temperature between about -10 and 100 C., l,2-dichloro-1,2-bis- (trifiuoromethyl)ethylene, N,N-dimethylaniline, and a metal cyanide.

7. The process which comprises reacting, at a temperature between about -10 and 100 C., l,2-dichloro-l,2-bis- (trifluoromethyl)ethylene, N,N-dimethylaniline, and an alkali metal p-toluenesulfinate. 1

8. The process which comprises reacting, at a temperature between about -10 and 100 C., l,2-dichloro-l,2-bistrifiuoromethyl ethylene, l, 1 -bis (p-dimethylaminophenyl)ethylene, and a metal cyanide.

9. The compound having the formula 1 7 18 10. The compound having the formula 12. The compound having the formula D'( :)|NCaH4C=O-GN p-(OHa)nN0eTI-C C0N C F; C F! 1): F2):

61 $1 11. The compound having the formula 13. The compound having the formula p a) 2N CfiHI O=C CN D-(CHx):N-C H C=CSO|CnH-C H;

No references cited. 

1. A COMPOUND OF THE FORMULA 